EP4076336A1 - Composition de remplissage de canal de racine dentaire - Google Patents

Composition de remplissage de canal de racine dentaire

Info

Publication number
EP4076336A1
EP4076336A1 EP20833819.4A EP20833819A EP4076336A1 EP 4076336 A1 EP4076336 A1 EP 4076336A1 EP 20833819 A EP20833819 A EP 20833819A EP 4076336 A1 EP4076336 A1 EP 4076336A1
Authority
EP
European Patent Office
Prior art keywords
group
root canal
paste
filling composition
dental root
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP20833819.4A
Other languages
German (de)
English (en)
Other versions
EP4076336B1 (fr
Inventor
Joachim E. Klee
Matthias Worm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dentsply Detrey GmbH
Dentsply Sirona Inc
Original Assignee
Dentsply Detrey GmbH
Dentsply Sirona Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dentsply Detrey GmbH, Dentsply Sirona Inc filed Critical Dentsply Detrey GmbH
Publication of EP4076336A1 publication Critical patent/EP4076336A1/fr
Application granted granted Critical
Publication of EP4076336B1 publication Critical patent/EP4076336B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/50—Preparations specially adapted for dental root treatment
    • A61K6/54—Filling; Sealing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/78—Pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/898—Polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • the present invention relates to a dental root canal filling composition, the use of such a dental root canal filling composition for a treatment or a prevention of an endodontic disease.
  • the present invention is further directed to a storage-stable two-pack den tal root canal filling composition making use of such an inventive dental root canal filling composition.
  • a polymerizable dental composition may be a dental adhesive compo sition, a bonding agent, a pit and fissure sealant, a dental desensitizing compo sition, a pulp capping composition, a dental composite, a dental glass ionomer cement, a dental cement, a dental root canal sealer composition, a root canal filling composition, or a dental infiltrant.
  • Dental compositions are desired to approach natural tooth structure with regard to strength and appearance. Accordingly, a great effort is documented by the prior art, which is directed to the development of dental compositions having improved properties with regard to physical properties, biocompatibility, aesthet ics and handling properties.
  • Dental compositions selected from a root canal filling composition and a pulp capping composition are subject to additional requirements in that the cured product is required to have a high radiopacity and in that the composition may not require external irradiation for curing.
  • a root canal filling composition or pulp capping composition contains radiopaque particulate fillers dispersed in a curable matrix.
  • the dispersion of radiopaque par ticulate fillers gives rise to a stability problem of the dispersions due to the high density of the filler and the low viscosity of the curable matrix.
  • the composition is cured by a thermal curing mechanism which may involve step growth polymerizing epoxide precur sor compounds.
  • a thermal curing mechanism which may involve step growth polymerizing epoxide precur sor compounds.
  • Prior art dental filling materials for tooth root canals have rela tively long setting time and may discolour.
  • the gold standard of dental root canal filling material which presently of fers the best overall properties, is AH Plus® from (Dentsply DeTrey, Kon stanz/Germany).
  • the good overall properties of AH Plus® especially concern physical and thermo-mechanical properties, curing properties like gelation time and handling properties like flow- and viscosity properties.
  • the good overall prop erties highly depend on the used filler composition and the structure of the epox ide-amine addition polymer, which is formed during the curing process of the AH Plus® composition.
  • the AH Plus® dental root canal filling composition consists of an amine paste and an epoxide paste.
  • the AH Plus® epoxide paste comprises Bisphenol A diglycidylether (CAS: 25068-38-6) as a main ingredient and the AH Plus® amine paste comprises the diamine N,N'-dibenzyl-5-oxanonandiamin-1 ,9 (OPC-91 , CAS: 113506-22-2) and the monoamine 1-aminoadamantane (CAS: 768-94-5) as main ingredients.
  • OPC-91 diamine N,N'-dibenzyl-5-oxanonandiamin-1 ,9
  • monoamine 1-aminoadamantane CAS: 768-94-5
  • thermomechanical properties of AH Plus have crucial impact on the performance of a dental root canal filling composition.
  • a dental root canal filling composition which shall exhibit a glass transition tem peratures T g in the range of 40 to 50°C and gelation times at body temperature below 16 h.
  • a dental root canal filling composition having all features of claim 1 .
  • Appropriate modifications to the inventive dental root canal filling composition are protected in dependent claims 2 to 13.
  • claim 14 comprises the use of such a dental root canal filling composition for a treat ment or a prevention of an endodontic disease.
  • Claim 15 comprises the use of such a dental root canal filling composition for a storage-stable two-pack dental root canal filling composition.
  • the present invention accordingly provides a dental root canal filling composition
  • a dental root canal filling composition comprising
  • At least one diamine at least one diamine; characterized in that the at least one primary monoamine comprises at least one cyclic non-aromatic hydrocarbon group and at least one, prefer ably one, primary amino group; wherein said at least one primary amino group is directly attached to said at least one cyclic non-aromatic hydrocarbon group; or wherein said at least one primary amino group is comprised by a hydro carbon moiety, which is directly attached to said at least one cyclic non aromatic hydrocarbon group.
  • the present invention offers alternative primary monoamines which can withstand any toxicological concerns while at the same time especially the characteristic thermomechanical properties of AH Plus can be maintained.
  • present invention provides a dental root canal filling compo sition, which exhibits a glass transition temperature T g in the range of 40 to 50°C and a gelation time at body temperature below 16 h.
  • substantially free means in the context of the present invention a concentration of less than 5 weight percent, preferably less than 2.5 weight percent, and more preferably less than 1 weight percent based on the total weight of the dental root canal filling composition.
  • the present invention is based on the recognition that a dental root canal filling composition comprising a primary monoamine as claimed provides a dental root canal filling composition, which has comparable and/or improved overall properties compared to the AH Plus® composition.
  • a dental root canal filling composition comprising such a primary monoamine as claimed provides a dental root canal filling composition having excellent properties with regard to physical and mechanical properties, biocompatibility, aesthetics and handling properties, having a high radiopacity, a high storage stability, a low shrinkage and flexibility, a relatively short setting time, and may be cured in the absence of light.
  • the dental root canal filling composition according to the present invention provides adjustable working and setting times, suitable viscosity, and shows no coloration problems.
  • a primary monoamine according to the present invention is adapted to act as a monomer which offers excellent reactivity, so that a dental root canal filling composition having excellent curing properties is provided. Furthermore, the use of the primary monoamine according to the present invention leads to a polymer having comparable and/or improved overall properties compared to the final pol ymer of the AH Plus® composition.
  • the present invention relates to a dental root canal filling composition com prising a specific primary monoamine.
  • a dental root canal filling composition in accordance with the invention is adapted to form epoxide-amine addition poly mers.
  • the dental root canal filling composition in accordance with the present invention is polymerizable and polymerizes to form a thermoplastic polymer.
  • polymerization and “polymerizable” relate to the combining by covalent bonding of a large number of smaller molecules, such as monomers, to form larger molecules, that is, macromolecules or polymers.
  • the monomers may be combined to form only linear macromolecules, or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.
  • difunctional monomers form linear polymers
  • monomers having at least three functional groups form crosslinked polymers also known as networks.
  • the amount of leachable monomers can be significantly re wreathd.
  • curing means the polymerization of functional polymerizable compounds such as monomers, oligomers or even polymers, into a polymer net work, preferably a crosslinked polymer network.
  • curable refers to dental composition that will polymerize upon mixing.
  • the working time is a period of time, meas ured from the start of mixing, during which it is possible to manipulate the root canal sealer.
  • the setting time is a period of time measured from the end of mixing at (37 ⁇ 1 ) °C and not less than 95 % relative humidity until the sealer does not show a mechanical impression using a Gilmore-type metric indenter.
  • the term "storage stability" as used herein means that the dental compo sition keeps its characteristics, in particular its working time and setting time, even after a long storage time of for example about 2 years.
  • the at least one cyclic non-aromatic hydrocarbon group is formed by three to nine, preferably by four to eight, more preferably by five to eight, ring-forming atoms.
  • at least one of the three to nine, pref erably of the four to eight, more preferably of the five to eight, ring-forming atoms of the cyclic non-aromatic hydrocarbon group is substituted by a linear or branched hydrocarbon group having 1 to 8 carbon atoms, which may be substi tuted by a hydroxyl group, a C1-6 alkoxy group, a C6-10 aryl group, a C6-10 aryloxy group, a C7-14 arylalkyl group, or a C7-14 arylalkoxy group.
  • Examples of such an inventive primary monoamine comprising at least one cyclic non-aromatic hydrocarbon group and at least one primary amino group; wherein said at least one primary amino group is directly attached to said at least one cyclic non-aromatic hydrocarbon group are:
  • the hydrocarbon moiety, which comprises the at least one primary amino group is attached to at least one ring-forming atom of the at least one cyclic non-aromatic hydrocarbon group; wherein said at least one ring forming atom is a carbon atom or a nitrogen atom.
  • Examples of such an inventive primary monoamine comprising at least one cyclic non-aromatic hydrocarbon group and at least one primary amino group; wherein said at least one primary amino group is comprised by a hydro carbon moiety, which is directly attached to said at least one cyclic non-aromatic hydrocarbon group, are:
  • At least one ring-forming atom of the at least one cyclic non-aromatic hydrocarbon group is a sulfur atom, an oxygen atom, or a nitrogen atom; with the proviso that the hydrocarbon moiety, which comprises the at least one primary amino group, is not attached to said at least one ring-forming atom.
  • the hydrocarbon moiety which comprises the at least one primary amino group, is a linear or branched alkyl, alkoxy, or alkenyl group; wherein preferably at least one carbon atom of the linear or branched alkyl, alkoxy, or alkenyl group is substituted by an oxygen, sulfur and/or a nitrogen atom.
  • alkyl group refers to a linear or branched saturated hydrocar bon chain of the respective length. This term can be exemplified by groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-pen- tyl, isopentyl, neopentyl, n-hexyl, n-decyl, dodecyl, tetradecyl, and the like. Such alkyl groups may be substituted further with one or more substituents such as alkylene, alkoxy, nitrile, aryl, cycloalkyl, and hydroxyl.
  • alkylene group refers to a linear or branched hydrocarbon chain of the respective length, which comprises at least one carbon-carbon dou ble bond. Such alkylene groups may be substituted further with one or more sub stituents such as alkyl, alkoxy, nitrile, aryl, cycloalkyl, and hydroxyl.
  • alkoxy group refers to a linear or branched hydrocarbon chain of the respective length, which comprises at least one oxygen atom in a ether structure inside of this alkoxy group (R-C-O-C-R).
  • alkoxy groups may be substituted further with one or more substituents such as alkyl, alkylene, nitrile, aryl, cycloalkyl, and hydroxyl.
  • the at least one primary monoamine further com prises at least one aromatic hydrocarbon group, wherein at least one of said ar omatic hydrocarbon groups is directly attached to the at least one cyclic non-ar- omatic hydrocarbon group.
  • the at least one diamine of the dental root canal filling composition is a disecondary diamine or a primary diamine, wherein prefer ably the dental root canal filling composition comprises at least one primary dia mine and at least one disecondary diamine.
  • a primary diamine in the context of the present invention is preferably a primary aliphatic diamine according to the following formula (III): wherein
  • Q’ represents a substituted or unsubstituted C3-20 alkylene group or a substi tuted or unsubstituted C3-20 cycloalkylene group, wherein the substituted C3-20 alkylene group and the substituted C3-20 cycloalkylene group may be substituted by one or more fluorine atoms, hydroxy groups, C1-6 alkyl groups, C3-12 cycloalkyl groups, a C1-6 alkoxy groups, a C1-6 alkylthio groups, a Ce-io aryl groups, a Ce-io aryloxy groups, a C7-14 arylalkyl groups, or a C7-14 arylalkoxy groups.
  • Q’ represents a substituted or unsubstituted C3-20 cycloalkylene group, more preferably Q’ represents a substi tuted cycloalkylene group, and even more preferably Q’ represents a substituted cycloalkylene group, wherein the substituents may be one or more C1-6 alkyl groups, C3-12 cycloalkyl groups.
  • the dental composition according to the present invention comprises a primary aliphatic diamine, which is selected from the group consisting of octahydro-4,7-methano-1 H-indenedimethylamine (CAS: 68889-71-4) and isophorone diamine (CAS: 2855-13-2).
  • a disecondary diamine in the context of the present invention is preferably a disecondary diamine according to the following formula (IV): wherein
  • A is a divalent substituted or unsubstituted C2-30 hydrocarbyl group
  • R 3 and R 4 which may be the same or different, independently represent a C1-10 alkyl group, a C3-10 cycloalkyl group, or a C6-11 arylalkyl group.
  • A is a divalent substituted or unsubstituted C2-30 hydrocarbyl group, which may contain up to 10 heteroatoms selected from the group consisting of N, 0, S, Si.
  • A is a divalent unsubstituted C2-30 hydrocarbyl group.
  • A is a divalent substituted C2-30 hydrocarbyl group, wherein the substituents are selected from the group consisting of a hydroxyl group, a tertiary amine group, a halogen atom, a C1-6 alkyl group, a C3-10 cycloalkyl group, a C1-6 alkoxy group, a C5-10 aryl group, a C6-11 arylalkyl group.
  • A represent a divalent substituted or un substituted C2-30 hydrocarbyl group, wherein the C2-30 hydrocarbyl group is a C2- 30 alkylidene group, a C3-10 cycloalkylidene group, a C7-30 arylalkylidene group.
  • R 3 and R 4 which may be the same or dif ferent, independently represent C1-10 alkyl group, a C3-10 cycloalkyl group, or a C6-11 arylalkyl group.
  • the C1-10 alkyl group, the C3-10 cycloalkyl group, or the C6-11 arylalkyl group may be substituted or unsubstituted.
  • the C1-10 alkyl group, the C3-10 cycloalkyl group, or the C6-11 arylalkyl group is unsubstituted.
  • the substituents are selected from the group consisting of a hydroxyl group, a tertiary amine group, a halogen atom, a C1-6 alkyl group, a C3-10 cycloal kyl group, a C1-6 alkoxy group, a C5-10 aryl group, or a C6-11 arylalkyl group.
  • the dental composition according to the pre sent invention comprises a disecondary diamine selected from the group consist ing of N,N’-dibenzylethylenediamine, N,N’-dibenzyl-3,6-dioxaoctandiamine-1 ,8, N,N’-dibenzyl-5-oxanonandiamine-1 ,9 (CAS: 113506-22-2), N,N’-dibenzyl- (2,2,4)trimethylhexamethylendiamine, N,N’-dibenzyl-(2,4,4)trimethylhexameth- ylendiamine, N,N’-dibenzylcyclohexylenediamine, N,N’-dibenzyl-xylylenedia- mine.
  • a disecondary diamine selected from the group consist ing of N,N’-dibenzylethylenediamine, N,N’-dibenzyl-3,6-dioxaoctandiamine-1
  • the dental root canal filling composition further com prises at least one rheological additive and/or rheological modifier, such as ethyl cellulose and cellulose acetate butyrate.
  • the dental root canal filling compo sition comprises an amine paste and an epoxide paste; wherein the amine paste or the epoxide paste comprises at least one rheological additive and/or rheologi cal modifier.
  • the dental root canal filling composition comprises an amine paste and an epoxide paste; wherein the amine paste and the epoxide paste each comprises at least one rheological additive and/or rheological modifier.
  • the at least one rheological additive and/or rheological modifier is a cellu lose derivate, which is selected from the group consisting of cellulose ether and cellulose ester.
  • ethyl cellulose (CAS 9004-57-3) as cellulose ether and cellulose acetate butyrate (CAS 9004-36-8), cellulose acetate propionate (CAS 9004-39- 1), cellulose acetate (CAS 9004-35-7) or cellulose propionate (CAS 9004-48-2) as cellulose ester are especially preferred.
  • the dental root canal filling composition comprises an amine paste and an epoxide paste; wherein the amine paste and the epoxide paste each comprises at least one rheological additive and/or rheo logical modifier; wherein the amine paste comprises at least one rheological ad ditive and/or rheological modifier, which is a cellulose ether, preferably ethyl cel lulose; and wherein the epoxide paste comprises at least one rheological additive and/or rheological modifier, which is a cellulose ester, preferably cellulose ace tate butyrate.
  • Cellulose ethers are especially preferred in the amine paste because un der certain circumstances, mainly depending on the overall composition of the respective amine paste, cellulose esters could cause in exceptional cases prob lems due to a possible undesired side reaction between the cellulose ester mol ecules and the reactive amine groups.
  • the dental root canal filling composition further com prises at least one filler, which is not a radio-opaque particulate filler.
  • the dental root canal filling compo sition comprises an amine paste and an epoxide paste; wherein the amine paste or the epoxide paste comprises at least one filler, which is not a radio-opaque particulate filler.
  • the dental root canal filling composition comprises an amine paste and an epoxide paste; wherein the amine paste and the epoxide paste each comprises at least one filler, which is not a radio-opaque particulate filler.
  • the at least one filler which is not a radio-opaque particulate filler, is a fumed silica, which is selected from the group consisting of Aerosil ® 200, Aero- sil ® R805 (CAS 92797-60-9), Aerosil ® R202 (CAS 67762-90-7 or CAS 541-02-6), CAB-O-SIL TS 720 (CAS 67762-90-7), Aerosil ® R8200 (CAS 68909-20-6), Aero- sil ® R812 (CAS 68909-20-6), Aerosil ® R972 (CAS 68611-44-9), and Aerosil ® R974 (CAS 68611-44-9).
  • the dental root canal filling composition comprises an amine paste and an epoxide paste; wherein the amine paste and the epoxide paste each comprises at least one filler, which is not a radio-opaque particulate filler; wherein the amine paste comprises at least one filler, which is not a radio-opaque particulate filler, which is Aerosil ® 200; and wherein the epox ide paste comprises at least one one filler, which is not a radio-opaque particulate filler, which is a fumed silica selected from the group consisting of Aerosil ® R805 (CAS 92797-60-9), Aerosil ® R202 (CAS 67762-90-7 or CAS 541-02-6), CAB-O- SIL TS 720 (CAS 67762-90-7), Aerosil ® R8200 (CAS 68909-20-6), Aerosil ® R812 (CAS 68909-20-6), Aerosil ®
  • Aerosil ® R805 (CAS 92797-60-9), Aero- sil ® R202 (CAS 67762-90-7 or CAS 541-02-6), CAB-O-SIL TS 720 (CAS 67762- 90-7), Aerosil ® R8200 (CAS 68909-20-6), Aerosil ® R812 (CAS 68909-20-6), Aer- osil ® R972 (CAS 68611-44-9), and Aerosil ® R974 (CAS 68611-44-9), are espe cially preferred in the epoxide paste because under certain circumstances, mainly depending on the overall composition of the respective epoxide paste, said hy drophobic Aerosils offer an additional stabilizing effect of the respective epoxide paste.
  • the dental root canal filling composition is substantially free, preferably completely free, of a compound of the following formula (I) wherein
  • R 1 is a fluorine atom, a hydroxyl group, an amino group, a Ci-6 alkyl group, a Ci-6 alkoxy group, a Ci-6 alkylthio group, a Ce-io aryl group, a Ce-10 aryloxy group, a C7-14 arylalkyl group, or a C7-14 arylalkoxy group; and
  • R 2 is a fluorine atom, a hydroxyl group, an amino group, a C1-6 alkyl group, a C1-6 alkoxy group, a C1-6 alkylthio group, a Ce-io aryl group, a C6-10 aryloxy group, a C7-14 arylalkyl group, or a C7-14 arylalkoxy group;
  • R 3 and R 4 which may be the same or different, independent from each other represent a fluorine atom, a C1-6 alkyl group, a C1-6 alkoxy group, a C1-6 alkylthio group, a Ce-io aryl group, a Ce-io aryloxy group, a C7-14 ar ylalkyl group, or a C7-14 arylalkoxy group, or R 3 and R 4 may be linked to gether and forming together with the carbon atom to which they are bonded a 3 to 6-membered saturated hydrocarbon ring;
  • R 5 is a hydroxyl group, an amino group, a C1-6 alkyl group, a C1-6 alkoxy group, a Ce-io aryl group, a Ce-io aryloxy group, a C7-14 arylalkyl group, or a C7-14 arylalkoxy group; provided that when n is 0, then at least one of R 1 , R 2 , R 3 /R 4 and R 5 , is present.
  • the dental root canal filling composition is substantially free, preferably completely free, of a compound having one of the following formulas: Rimantadine 1 -Aminoadamantane
  • the at least one di- or polyepoxide is a compound of the following formula (II): wherein
  • Q is a (m+1 )-valent organic group
  • R 6 , R 7 and R 10 which may be the same or different and which are independent from each other, represent a hydrogen atom, or a C1-6 alkyl group
  • the R 8 , R 9 and R 11 which may be the same or different and which are independent from each other, represent a hydrogen atom, or a C1-6 alkyl group
  • m is an integer of from 1 to 3.
  • Q represents an (m+1 )-valent organic group.
  • Q represents a 2-valent organic group, or a 3-valent organic group, and more preferably, Q represents a 2-valent organic group.
  • the (m+1)-valent organic group may be a group having a total of 1 to 40 carbon atoms, preferably 2 to 20 carbon atoms.
  • the organic group may include an aliphatic, alicyclic, or aromatic moiety or a combination of two or more of such moieties.
  • the organic group may further include one or more functional groups such as amide groups, ester groups, urethane groups, urea groups, keto groups, ether groups, thioether groups, carbonate groups, or tertiary amino groups, which link two or more aliphatic, alicyclic, or aromatic moieties.
  • the organic group may be substituted by one or more substituents selected from hydroxyl groups, halogen atoms, a Ci-6 alkyl group, a Ci-6 alkoxy group, a Ci-6 alkylthio group, a Ce-io aryl group, a Ce-io aryloxy group, a C7-14 arylalkyl group, or a C7-14 arylalkoxy group.
  • substituents selected from hydroxyl groups, halogen atoms, a Ci-6 alkyl group, a Ci-6 alkoxy group, a Ci-6 alkylthio group, a Ce-io aryl group, a Ce-io aryloxy group, a C7-14 arylalkyl group, or a C7-14 arylalkoxy group.
  • the (m+1)-valent organic group may include alicyclic or aro matic moiety, and more preferably the (m+1 )-valent organic group includes an aromatic moiety.
  • Q represents the following group:
  • m is an integer of from 1 to 3.
  • m is an integer of from 1 to 2, and more preferably m is 1 .
  • R 6 , R 7 and R 10 which may be the same or different and which are independent from each other, represent a hydrogen atom, or a Ci-6 alkyl group.
  • R 6 , R 7 and R 10 represent a hydrogen atom.
  • all three of R 6 , R 7 and R 10 represent a hydro gen atom.
  • the R 8 , R 9 and R 11 which may be the same or different and which are independent from each other, represent a hydrogen atom, or a Ci-6 alkyl group. Furthermore, in a compound of formula (II), if more than one R 8 is present, the more than one R 8 may be different. In a compound of formula (II), if more than one R 9 is present, the more than one R 9 may be different. In a compound of formula (II), if more than one R 11 is present, the more than one R 11 may be different.
  • R 8 , R 9 and R 11 represent a hydrogen atom. In a particularly preferred embodiment, all of the R 8 , R 9 and R 11 moieties which are present are hydrogen atoms.
  • the compound according to formula (II) is Bisphenol A Diglycidylether (CAS: 25068-38-6), or Bis-[4-(-2,3-epoxypro- poxy)phenyl]-methane (CAS: 9003-36-5).
  • the dental root canal filling composition further com prises an aliphatic polyamine selected among compounds of the following struc tures:
  • R 12 is hydrogen or a substituted or unsubstituted C1-18 alkyl group, a substituted or unsubstituted C3-18 cycloalkyl group, or a substituted or unsubstituted C7-18 aryalkyl group,
  • R 13 is a difunctional substituted or unsubstituted Ci to C18 alkylene group, or a substituted or unsubstituted cycloalkylene group,
  • A’ is a moiety derived from a compound that is capable of an addition reaction with amines such as di- or polyepoxides, and c is an integer.
  • R 12 is hydrogen, a substituted or unsubstituted C3-18 cycloalkyl group, or a C7-18 ar- ylalkyl group. More preferably, R 12 is a substituted or unsubstituted C3-18 cycloal kyl group, or a substituted or unsubstituted C7-18 arylalkyl group. Even more pref erably, R 12 is a substituted or unsubstituted C7-18 arylalkyl group. In a particularly preferred embodiment, R 12 is an unsubstituted C7-18 arylalkyl group.
  • R 13 is difunctional substituted or unsubstituted Ci to C18 alkylene group, more prefer ably R 13 is a difunctional unsubstituted Ci to C18 alkylene group.
  • A’ is a moiety derived from a compound that is capable of an addition reaction with amines such as di- or polyepoxides.
  • A’ is a moiety derived from an addition reaction of a di- or polyepoxide according to formula (II) and an amine. More preferably, A’ is a moiety derived from an addition reaction of an amine with a compound of formula (II) which is a diepoxide.
  • A’ is a moiety derived from an addition reaction of an amine and a compound of formula (II) which is a diepoxide, and wherein in the compound of formula (II) Q represents the following structures:
  • c is an inte ger.
  • c is an integer of from 1 to 10, more preferably c is an integer of from 2 to 8, even more preferably c is an integer of from 4 to 6.
  • the dental root canal filling composition further com prises at least one radio-opaque particulate filler, preferably at least CaWC as the at least one particulate filler.
  • the radiopaque particulate filler usually has an average particle size of from 0.005 to 100 pm, preferably of from 0.01 to 40 pm as measured using, for example, by electron microscopy or by using a conventional laser diffraction par ticle sizing method as embodied by a MALVERN Mastersizer S or MALVERN Mastersizer 2000 apparatus.
  • the radiopaque particulate filler may be a multi modal radiopaque particulate filler representing a mixture of two or more radio paque particulate fractions having different average particle sizes.
  • the radio paque particulate filler may also be a mixture of particles of different chemical composition.
  • the radiopaque filler in the form of a particulate filler or a nanofiller may be selected from any of the zinc, ytterbium, yttrium, gadolinium, zirconium, strontium, tungsten, tantalum, thorium, niobium, barium, bismuth, molybdenum and lantha num metals, alloys thereof, organometallic complexes thereof, oxides, sulfates, carbonates, halides, oxy-halides, subnitrates, tungstates and carbides thereof, iodine and inorganic iodides, either singly or in combination.
  • the radiopaque filler is selected from any of bismuth trioxide, bismuth carbonate, bismuth oxy-chloride, bismuth subnitrate, zirconium oxide, barium sul fate, barium tungstate and calcium tungstate, either singly or in combination.
  • the radiopaque filler is selected from bar ium tungstate and calcium tungstate, either singly or in combination.
  • the radiopaque filler is calcium tungstate.
  • the dental composition according to the present invention preferably com prises 1 to 85 percent by weight, more preferably 40 to 85 percent by weight, even more preferably 40 to 70 percent by weight, of the radiopaque particulate filler, based on the weight of the entire composition.
  • the viscosity and thixotropicity of the uncured as well as the physical prop erties of the cured compositions may be controlled by varying the sizes and sur face areas of the filler.
  • the filler may be surface treated with one or more silanating agents.
  • silanating agents include those having at least one polymerizable double bond and at least one group that easily hydrolyses with water. Examples of such agents include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl- dimethoxy-monochlorosilane, 3-methacryloxypropyldichloromonomethoxysilane, methacryloxypropyltri-chlorosilane, 3-methacryloxypropyldichloromonomethyl- silane, 3- methacryloxypropylmonochlorodimethylsilane, or 2,3-epoxypropyltri- methoxysilane, aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane and mixtures thereof.
  • the present invention also claims the use of such an inventive dental root canal filling composition for a treatment or a prevention of an endodontic disease.
  • the object of the present invention is also solved by a storage- stable two-pack dental root canal filling composition comprising a first paste and a second paste, wherein the dental root canal filling composition is a composition as defined by one of the preceding claims 1 to 13.
  • the storage-stable two-pack dental root canal filling composition is provided in a double chamber cartridge, wherein said double chamber cartridge is made of a polymeric material, preferably made of polypropylene or polybutyleneterephthalate, especially preferred made of poly- butyleneterephthalate.
  • the double chamber cartridge out of polybutyleneterephthalate, which provides in general superior barrier properties (compared to polypropylene) of the two chambers against possible oxygen mi gration; and especially against the migration of coloring components of the amine paste composition into the chamber material.
  • the at least one di- or polyepoxides have a dynamic viscosity at 23 °C of less than 30 Pa * s.
  • the dental root canal filling composition has a gelation time of less than 25 hours, preferably less than 20 hours, and more preferably less than 16 hours.
  • the dental root canal filling composition has a glass transition temperature T g ranging from 38 to 80°C, preferably from 39 to 60°C, and more preferably from 40 to 50°C.
  • the present invention thus addresses the problem of providing a suitable alternative of primary monoamines as part of a dental root canal filling composi tion, which allows mimicking of the characteristic AH Plus paste properties in terms of setting kinetics, thermomechanical behavior and handling properties (flow, film thickness).
  • DSC Densired Scanning Calorimetry
  • the cured samples were portioned to individual masses of 4.5 - 5.5 mg and transferred into aluminum crucibles (diameter: 6 mm) for DSC characteriza tion.
  • Measurements were performed on a DSC 204 F1 Phoenix (Netzsch-Gerate- bau GmbH) using a heat flow of 30 K/min for heating and cooling cycles. Analysis was performed using the software Netsch Measurement, Netsch ASC Manager (auto sampling), Netsch Proteus (analysis).
  • the mixed pastes exhibit a gelation time of less than 15 h (method described above), flow of 22 mm (according to ISO 6876:2012), film thickness of 17 ⁇ 2 pm (according to ISO 6876:2012).
  • Epoxide Paste A1 and Amine Paste A1 were mixed in a ratio of 1.0000:1.1103 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 15 h 20 min (SAR5- 50-01 ), flow (according to ISO6876:2012): 21 .2 mm (SAR5-51 -01 ), film thickness (according to ISO6876:2012): 10 pm (SAR5-52-01 ).
  • Epoxide Paste A2 and Amine Paste A2 were mixed in a ratio of 1.0000:1.0335 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 14 h 5 min (SAR5- 29-02), flow (according to ISO6876:2012): 23.0 mm (SAR5-25-01), film thickness (according to ISO6876:2012): 17 pm (SAR5-27-02). Glass transition temperature (cured for 2 weeks at 37°C): 47.3 °C (MAW1 -16-01 ).
  • Cyclopentylamine (0.7400 g, 8.6905 mmol), OPC-91 (1.6679 g, 4.8981 mmol), TCD-Amine (0.0996 g, 0.5126 mmol), CaW0 4 (9.6335 g), Zr0 2 (2.4128 g), Aer- osil ® 200 (0.2921 g) and Baysilone M-500 (0.1618 g) were transferred into a speed mixer container and mixed for 5 min with 2150 rpm. The paste was man ually mixed with a spatula followed by another speed mixer run (1 min, 2150 rpm) to afford a homogenous, white paste.
  • Epoxide Paste A3 and Amine Paste A3 were mixed in a ratio of 1.0000:0.8110 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 14 h 5 min (SAR5- 30-04), flow (according to ISO6876:2012): 21.8 mm (SAR5-27-01), film thickness (according to ISO6876:2012): 9 pm (SAR5-29-02).
  • Glass transition temperature (cured for 2 weeks at 37°C): 41 .8 °C (MAW1 -16-01 ).
  • Epoxide Paste A4 and Amine Paste A4 were mixed in a ratio of 1.0000:1.1104 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 15 h 20 min (SAR5- 50-02), flow (according to ISO6876:2012): 20.0 mm (SAR5-51-02), film thickness (according to ISO6876:2012): 9 pm (SAR5-52-02). Glass transition temperature (cured for 2 weeks at 37°C): 44.9 °C (MAW1 -17-01 ).
  • Epoxide Paste A5 and Amine Paste A5 were mixed in a ratio of 1.0000:0.9518 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 14 h 5 min (SAR5- 30-01 ), flow (according to ISO6876:2012): 21.2 mm (SAR5-26-01), film thickness (according to ISO6876:2012): 14 pm (SAR5-28-01 ). Glass transition temperature (cured for 2 weeks at 37°C): 42.6 °C (MAW1 -18-01 ).
  • Cycloheptylamine (0.7415 g, 6.5504 mmol), OPC-91 (1.6683 g, 4.8993 mmol), TCD-Amine (0.0949 g, 0.4884 mmol), CaW0 4 (9.6321 g), Zr0 2 (2.4120 g), Aer- osil ® 200 (0.2935 g) and Baysilone M-500 (0.1585 g) were transferred into a speed mixer container and mixed for 5 min with 2150 rpm. The paste was man ually mixed with a spatula followed by another speed mixer run (1 min, 2150 rpm) to afford a homogenous, white paste.
  • Epoxide Paste A6 and Amine Paste A6 were mixed in a ratio of 1.0000:0.9518 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 14 h 5 min (SAR5- 30-02), flow (according to ISO6876:2012): 21 .8 mm (SAR5-26-02), film thickness (according to ISO6876:2012): 13 pm (SAR5-28-02). Glass transition temperature (cured for 2 weeks at 37°C): 42.6 °C (MAW1 -18-01 ).
  • Cyclooctylamine (0.7415 g, 5.8280 mmol), OPC-91 (1.6677 g, 4.8975 mmol), TCD-Amine (0.0981 g, 0.5049 mmol), CaW0 4 (9.6344 g), Zr0 2 (2.4145 g), Aer- osil ® 200 (0.2926 g) and Baysilone M-500 (0.1583 g) were transferred into a speed mixer container and mixed for 5 min with 2150 rpm. The paste was man ually mixed with a spatula followed by another speed mixer run (1 min, 2150 rpm) to afford a homogenous, white paste.
  • Epoxide Paste A7 and Amine Paste A7 were mixed in a ratio of 1.0000:1.0105 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 14 h 5 min (SAR5- 30-03), flow (according to ISO6876:2012): 20.5 mm (SAR5-26-03), film thickness (according to ISO6876:2012): 8 pm (SAR5-28-03).
  • Glass transition temperature (cured for 2 weeks at 37°C): 44.2 °C (MAW1 -19-01 ).
  • Epoxide Paste A8 and Amine Paste A8 were mixed in a ratio of 1.0000:1.0838 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 15 h 20 min (SAR5- 50-03), flow (according to ISO6876:2012): 20.3 mm (SAR5-51-03), film thickness (according to ISO6876:2012): 8 pm (SAR5-52-03). Glass transition temperature (cured for 2 weeks at 37°C): 48.9 °C (MAW1 -19-01 ).
  • Epoxide Paste B1 Bisphenol A diglycidyl ether (8.1214 g) and bisphenol F diglycidyl ether (1.0264 g) transferred into a speed mixer container and mixed for 5 min with 2150 rpm.
  • CaW04 Grade B (10.3636 g) and CaW04 (10.3636 g), Aerosil®200 (0.086 g) and SICOVIT® (Yellow 10 E172) (0.0456 g) were added and speed mixing was applied (5 min, 2150 rpm).
  • the paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, light yel low paste.
  • the mixed pastes exhibit a gelation time of less than 15 h, flow of 21 mm, film thickness of 13 mm (all according to ISO 6876) and glass transition temperature of 45 ⁇ 2 °C (DSC) after curing for 2 weeks at 37°C.
  • Epoxide resins and cellulose ester / ether is dispersed in T range from 40 - 100°C. Clear resins can be achieved within 10 min - 10 h. Ultra-turrax agitation can used to promote dispensing.
  • Epoxide Premixture 1 (4.349 g) and CaW04 (10.589 g), Aerosil®200 (0.042 g) and SICOVIT® (Yellow 10 E172) (0.021 g) were added and speed mixing was applied (5 min, 2150 rpm). The paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, light yel low paste.
  • Amine resin and cellulose ether is dispersed in T range from 40 - 120°C. Clear resins can be achieved within 10 min - 12 h. Ultra-turrax agitation can used to promote dispensing.
  • Amine Premixture 1 (2.504 g) and CaW04 (12.046 g), Aerosil®200 (0.270 g) and Baysilone M500 (0.180 g) were added and speed mixing was applied (5 min, 2150 rpm). The paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, white paste.
  • the mixed pastes exhibit a gelation time of less than 15 h, flow of 22 mm, film thickness of 16 mm (all according to ISO 6876) and glass transition temperature of 44 ⁇ 2 °C (DSC, after curing for 2 weeks at 37°C.
  • Epoxide Premixture 1 (4.349 g) and CaW04 (10.589 g), Aerosil R202 (0.042 g) and SICOVIT® (Yellow 10 E172) (0.021 g) were added and speed mixing was applied (5 min, 2150 rpm). The paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, light yel low paste.
  • Amine Premixture 1 (2.504 g) and CaW04 (12.046 g), Aerosil®200 (0.270 g) and Baysilone M500 (0.180 g) were added and speed mixing was applied (5 min, 2150 rpm). The paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, white paste.
  • the mixed pastes exhibit a gelation time of less than 15 h, flow of 22 mm, film thickness of 16 mm (all according to ISO 6876) and glass transition temperature of 45 ⁇ 2 °C (DSC, after curing for 2 weeks at 37°C.
  • Epoxide Premixture 1 (4.349 g) and CaW04 (10.589 g), Aerosil 200 (0.042 g) and SICOVIT® (Yellow 10 E172) (0.021 g) were added and speed mixing was applied (5 min, 2150 rpm). The paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, light yel low paste.
  • the mixed pastes exhibit a gelation time of less than 15 h, flow of 22 mm, film thickness of 16 mm (all according to ISO 6876) and glass transition temperature of 47 ⁇ 2 °C (DSC, after curing for 2 weeks at 37°C.
  • the paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, light yellow paste.
  • the mixed pastes exhibit a gelation time of less than 15 h, flow of 23 mm, film thickness of 13 mm (all according to ISO 6876) and glass transition temperature of 46 ⁇ 2 °C (DSC) after curing for 2 weeks at 37°C.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Chemical & Material Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Dental Preparations (AREA)
  • Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)

Abstract

La présente invention concerne une composition de remplissage d'un canal de racine dentaire comprenant au moins un di- ou polyépoxyde ; au moins une monoamine primaire ; et au moins une diamine ; la au moins une monoamine primaire comprenant au moins un groupe hydrocarboné cyclique non aromatique et au moins un groupe amino primaire ; ledit au moins un groupe amino primaire étant directement fixé audit au moins un groupe hydrocarboné cyclique non aromatique ; ou ledit au moins un groupe amino primaire étant composé d'une fraction hydrocarbonée, qui est directement fixée audit au moins un groupe hydrocarboné cyclique non aromatique.
EP20833819.4A 2019-12-17 2020-12-17 Composition de remplissage de canal de racine dentaire Active EP4076336B1 (fr)

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EP19217246 2019-12-17
PCT/EP2020/086720 WO2021122957A1 (fr) 2019-12-17 2020-12-17 Composition de remplissage de canal de racine dentaire

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EP (1) EP4076336B1 (fr)
JP (1) JP2023506909A (fr)
CN (1) CN114929178A (fr)
AU (1) AU2020410373A1 (fr)
CA (1) CA3164598A1 (fr)
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SE9802360D0 (sv) * 1998-07-01 1998-07-01 Wikstroem Hakan Vilhelm New 2-aminothiazol-fused 2-aminoindans and 2-aminotetralins ((basic)-N-substituted and (basic)-N,N-disubstituted derivatives of 2,6-diamino-thiazolo(4,5-f)indan and 2,7-di-amino-thiazolo(4,5-g)tetralin
DE102012003117A1 (de) * 2012-02-16 2013-08-22 Heinrich-Heine-Universität Düsseldorf Antimikrobielle Füllmaterialmischung
EP2963025B1 (fr) * 2014-07-02 2020-01-22 DENTSPLY DETREY GmbH Composition dentaire
WO2016044918A1 (fr) * 2014-09-24 2016-03-31 Apotex Inc. Procédés de préparation de rotigotine et ses intermédiaires
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AU2020410373A1 (en) 2022-06-16
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US20230014155A1 (en) 2023-01-19
WO2021122957A1 (fr) 2021-06-24
EP4076336B1 (fr) 2024-05-15

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